Comparative vibrational spectroscopic studies, HOMO–LUMO and NBO analysis of 5,7-dibromo-8-hydroxyquinoline and 5,7-dichloro-8-hydroxyquinoline based on Density Functional Theory
Highlights
► Hydroxyquinoline derivatives are used as antimalarial and anticancer drugs. ► Vibrational bands of DBHQ and DCHQ were obtained by the B3LYP/6-311++G**. ► NBO, Mulliken charges and other parameters have been reported. ► A comparison with the IR and Raman spectra of DBHQ and DCHQ has been reported. ► The electronic properties, HOMO and LUMO energies and ESP also studied.
Introduction
Quinoline, is an aromatic nitrogen compound characterized by a solid-ring structure contains a benzene fused to pyridine at two adjacent carbon atoms. Quinoline derivatives are used as catalyst, corrosion inhibitor, preservative and as solvent for resins and terpenes. They are used in transition-metal complex catalyst chemistry for uniform polymerization and luminescence chemistry. They are used as antifoaming agent in refinery field. Quinaldine, 2-methylquinoline are used as an anti-malarial and preparing other anti-malarial drugs. It is used in manufacturing oil soluble dyes, food colorants, pharmaceuticals, pH indicators and other organic compounds. Hydroxyquinoline and its derivatives are bacterial inhibitor and precursor of a number of anti-malarial and anticancer drugs [1], [2].
Literature survey reveals that detailed interpretations of the infrared spectra have been reported on halogen substituted hydroxy quinoline [3]. But the results based on quantum chemical calculations and FT-IR, FT-Raman spectral studies, the HOMO–LUMO and NBO analyses on 5,7-dibromo-8-hydroxyquinoline (DBHQ) and 5,7-dichloro-8-hydroxyquinoline (DCHQ) have no reports. This inadequacy observed in the literature encouraged us to make this theoretical and experimental vibrational spectroscopic research based on the structure of molecules to give a correct assignment of the fundamental bands in experimental FT-IR, FT-Raman spectra. Along with the vibrational spectra, the electrostatic potential should help us to understand the structural and spectral characteristic and bioactivity of compounds of this class.
In the present work, we have attempted to study the HOMO–LUMO, NBO analysis, the thermodynamical functions and polarizability of DBHQ and DCHQ by using B3LYP level of theory throughout with the 6-311++G** basis set implemented in the Gaussian 09 program suite [4]. Geometries obtained from DFT calculation were then used to perform NBO analysis.
Section snippets
General method
The fine samples of DBHQ and DCHQ were obtained from Lancaster Chemical Company, UK and used as such for the spectral measurements. The FT-Raman spectra of DBHQ and DCHQ were recorded using 1064 nm line of Nd:YAG laser as excitation wave lengths in the region 3500–100 cm−1 on thermo electron corporation model NEXUS670 spectrometer equipped with FT-Raman module accessory. The FT-IR spectrum of the title compounds were recorded in the region 4000–400 cm−1 on Perkin Elmer Spectrophotometer in KBr
Geometric structure
The optimized molecular structures of the DBHQ and DCHQ belong to C1 point group symmetry with numbering schemes is presented in Fig. 1, Fig. 2, respectively. The existences of two rotational isomers between pyridine and hydroxyl groups (O-cis and O-trans) in DBHQ and DCHQ have been demonstrated. The energy values of cis and trans for DBHQ −5624.3432 hartrees (−14766714.319 kJ/mol) and −5624.3435 hartrees (−14766714.5572 kJ/mol) and for DCHQ are −1396.5023 hartrees (−3666517.0792 kJ/mol) and
Mulliken population analysis: Mulliken atomic charge
Mulliken atomic charge calculation [44] has an important role in the application of quantum chemical calculation to molecular system. Atomic charges affect dipole moment, polarizability, electronic structure and more properties of molecular systems. The total atomic charges of DBHQ and DCHQ obtained by Mulliken population analysis with 6-311++G** basis set are listed in Table. 5. From the result it is clear that the substitutions of Br, Cl and OH atoms in the heteroaromatic ring leads to a
Conclusion
A complete vibrational assignment for DBHQ and DCHQ have been proposed, aided by the B3LYP method using 6-311++G** basis set and PED analysis. FT-IR and FI-Raman spectra of DBHQ and DCHQ molecules have been recorded. The optimizations of the relative orientation of the bromine, chlorine, and hydroxyl group of the DBHQ and DCHQ, respectively leads to two forms, O-cis and O-trans with O-trans being more stable in both DBHQ and DCHQ. The theoretically computed wavenumbers were found good agreement
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